Azo dyestuffs



Patented Aug. 23, 1949 UNITED PATENT OFFICE A'ZO DYESTUFFS Frledrich'Felixw and Alphonsefieckendorn, Basel, Switzerland; asslgnoi's to GibaeLimited, Basel,

Switzerland Ric thawin Application anuary 7, 1946, s rial- No. 639,709; In Switzerland January 25,

aoiai s, (01. 260-197) It: has; been found that valuable azoedyestuifs:

are}: ohtainedl couplinga hydroxynaphthalene, which is, alklyatedin the nucleus, with a diazo cempoundin suchamanner as to efi'ect; the coupling of. the dime-compound in orthoepositionwith respect to the hydroxy group, the chosen in additibn to at least oneOH' gi-ou'p contain at least one alkyl radical linked directly to the naphthalene nucleus, the orthopositicn with respect to the oer-group (i. e. the 2-position in the ease of I-h3rdroXynaphtIialene and the-l-positl'o'n in the case of 2'-hydroxynaphthalene) al ways remaining ir'ee.

Examples of such compounds area-mammhydroxynaphthalene, 4-ethyl 1 hydroxynaphthalene, 4-n-butyl-l hydroxynaphthalene, 4-isobutyl-l-hydroxynaphth.alene... 4-secondary butyll-hydroxynaplithalene, 4-tertiary butyl-l-hydroxynaphthalene, 4 amyl-l-hydroxivnaphthalene, 4 isoamyl 1 hydroxynaphthalene, 4-tertlary amyl 1 hydrexynaphthaiene, 4 a ethylpropyl 1 hydroxynaphthalene, 4 a methylbutyl-l hydroxyiiaphthalene; 5 methyl-{l -hydi'ox$ naphthalene, s metnylz hydroxynaphthm lene; 5'-methyl=z hydroxynaphthalene, o-m'ethyl 2=h3 drpxynaphthalene 8 'ai'he'thyl '2 hydroxynaphthalene, 6-ethyl-2-hydroxynaphthalene, 3- isobutyl-2=hydroxynaphthalene, 3 secondary bum l-:2-hydroxynaphthalene, 3-isoamyl-2mydmxynaphthalene, 3,"-'(1" etlnglprop3 1) -z-hyclroxynaphth'aiene, 3'- l"=methylbutyl) -2-hydroxynaphthalane, 3- (2-methylbutyl) -2-hydroxynaphthalene, 3'-tertiary 'a'myl-2=hydi'oxy aplithalen'e, 4'z6 -d'imethyll-hydroxynaphthalene, '3 41-dimet'hyl-1- hyd'r'oxynaphthalene, 3}7 diinethyl-z-hydroxynaphthalene, 3:6 dimethyl-z-hydroxynap1ithalene,v 4 methyl-6-isopropyle2-hydroxynaphtharlehi... 3:517 tr'i'm'ethyl 2 hydroxynaphthalcne. (compare or, instance U; S.. Patents Nos. 2,073,!!96 and 2073,9971) Furthermore, there may beiused cycloalkylated hydroxynaphthalenes, such as, for example, 4-cyc1ohexyl-1-hydroxynaphthalene and 6,-cyclohexyl-2-hydroxynaphthalene. The hydrox-ynaphthalenes, which are alkylated in the nucleus and are, serving as starting materials for the present. process may as Well be further substituted, for instance by sulfo groups, halogen atoms and the like.

Of the hydroxynaphthalenes which are alkylated in the nucleus those are of special advantage, Whose alkyl radical contains more than one carbon atom, and among these compounds the corresponding 4-alkyl-l-hydroxynaphthalenes.

As diam-compounds there may be used above.

all those which are derived from amines which in.

ortho-position with respect to the NHz-group, carrya substituent capable of participating in the formation of metal complexes in the finished dyestufi. Such substituents are, for instance,

preferably the OH-group, then the COOK-group, and; finally other atom groupings, for example, the O.CH2COOH-, the S-CI-h, the

S--CH2COOH-groups and the like. From among such amines there may be mentioned above all, ortho-aminophenols or ortho-aminonaphthols, like 1-hydroxy-2- amino-benzene, l-hydroxy-2-amino 4 chlorobenzene, 1-hydroxy-2-amino-4-nitrobenzene, 1-

hydroxy 2-amino-5-nitrobenzene,. l-hydroxy-2 amino-4: S-dinitrobenzene, l hydroxy-tZ-amino- 4-nitro-6-chlorobenzene, 1-hydroxy-2-amino-4- chlom-G-nitrobenzene, l-hydroxy-2-amino-4 5- dichlorobenzene, 1 hydroxy-2-alnino-3:4z5-trichlorobenzene, sulfonic acids or carboxylic acids of such compounds, like 1-hydroxy-2-aminobenzene-4-sulfonic acid, 1-hydroxy-2-aminobenzene- 4-carboxylic acid, 1-hydroxy-2-aminobenzene-G- carboxylic acid, 1 -hydroxy-2-amin0-6-chloro- ,b'enzene --4-sulionic acid, 1-hydroxy-2-amino-4- chlorobenzene-fi-sulfonic acid, 1-hydroxy-2-ami no-fi' nitrobenzene-4-sulfonic acid, 1-hyd'roxy-2- amino-4-nitrobenzene 6 sulfoni'c acid, 1 hydifoxy-Z-amino-'fi-nitrobenzene 4 sulfonic acid, 1-hydroxy-2-aminobenzene 4 sulfonic acid-6- carboxylic acid, 1 amino-Z-hydroxy-naphtha- In. addition to, the diam-compounds which are I ness properties.

with respect to the NHz-group contain an esteri- Y fled or etherified hydroxyl group or a substituent,

for instance a halogen atom, which may be replaced by an OH-group. From among such amines there may be mentioned the acid Eulfuric acid esters of the ortho-aminophenols or ortho-aminonaphthols mentioned in the preceding paragraph, for instance the acid sulfuric acid ester of l-hydroxy-Z-aminobenzene or of 1-hydroxy-2-amino 4 chlorobenzene, the corresponding alkylethers and their sulfonie acids, for example, l-methoxy-2-aminobenzene, l-methoxy-2-amino-4 nitrobenzene, 1 methoxy 2 aminobenzene-l-sulfonic acid, and the like, furthermore l-ch1oro-2-aminobenzene, lA-dichloro-2-aminobenzene, 1-chloro-2-aminobenzenel-sulfonic acid, and the like.

The coupling is carried out advantageously in an alkaline, preferably a caustic alkaline medium. When the substituents in the hydroxynaphthalene derivative which is alkylated in the nucleus are arranged in such a manner that coupling doesnot necessarily have to take place in ortho-position to the OI-I-group, the coupling may be'caused to take the desired course through the use of a suitable diazo-compound (in the case of l-hydroxynaphthalenes which are alkylated in the nucleus and which carry no substituents in 3-, 4- or 5-position by the use of diazotized orthoaminonaphthols for instance) or through the use of suitable concentration and alkalinity conditions. When diazo-compounds which are esterified at the OH-group standing in ortho-position have been used to prepare the dyestuffs, and if these dyestuifs are to be used as after-chroming dyestuffs, they are converted into ortho:ortho'- dihydroxyazo-dyestuffs by treatment with saponifying agents.

Depending upon the components used, the new dyestuffs may serve either for dyeing or printing of a very wide variety of fibers of vegetable or animal origin. Especially valuable are the dyestuffs of the general formula wherein R1 is an aromatic radical of the benzene or naphthalene series carrying a hydroxyl group in oposition to the N=N-group and R represents an alkyl radical containing more than 1 carbon atom, such as ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl or cyclohexyl radicals, and the like. These dyestuffs are especially suited for the dyeing of animal fibers.

If components are used which contain no sulfogroups, products are obtained which by treatment with agents yielding metal, are converted into metalliferous pigments which are used to dye lacquers.

If the new dyestuffs corresponding to the foregoing general formula are prepared from diazo components which contain in ortho-position to the diazo group a 'hydroxy group or a carbcsyl group and if the components are so chosen as to obtain dyestuffs with at least one sulfo group, these dyestuffs are especially suitable for dyeing wool in fast shades because after-chroming or dyeing in presence of chrome mordants will lead to dyeings which in" addition ,to their excellent fastness to light also have excellent wet fast- Among these dyestuffs, those which contain the sulfo group in the diazotizing components are especially valuable.

By treating these dyestuffs with agents yielding metal, preferably agents yielding chromium,

but also other agents yielding metal, like copper, nickel, or cobalt compounds or mixtures of such products, acid dyestuffs are obtained which are suitable for the dyeing of animal fibers or fibers which have an aflinity for acid dyestufis,

Similar products are obtained if azo-dyestufis are prepared from the diazotized amines which weight to parts by volume being the same as that of the kilogram to the liter.

Example 1 20 parts of 4-butyl-l-hydroxynaphthalene are dissolved in 75v parts of water and 15 parts by volume of caustic soda solution of 30 per cent. strength to give a'clear solution, to which 18 parts of sodium'carbonate are added. Then a diazo solution, prepared in the usual manner from 23.4 parts of l-hydroxye2-amino+i-nitrobenzene-6- sulfonic acid is added to the solution of the coupling component. Coupling takes place instantly. The wholeis stirred for six hours whereupon the separated dyestuff is filtered off with suction. In order to-be purified, it is taken up in water again, stirred, then suction-filtered and dried. The dyestuff which in its free state corresponds to the formula om-om-om-bm is a dark powder which dissolves in water with a violet coloration and dyes wool in greenish olive tints, bothby the aft'er-chroming process and if chromed during the dyeing process. The dyeings obtained are remarkable for their very good wet fastnessprop'erties and especially their good fastness .to light. The replacement of l-butyl-l-hydroxy-naphthalene by 4-ethyl-1-hydroxynaphthalene leads to chroming dyestuifs which also give olivedyeings. i

A' similar dyestuff, which dyes wool in both chroming processes in blue-gray tints, is obtained if as diazocomponent 22.4 parts of l-hydroxy- 2-amino-4-chlorobenzene-G-sulfonic acid and as coupling component 20 parts of 4-butyl-l-hydroxynaphthalene are used, and another similar dyestufi is obtained by using 4'-ethyl-l-hydroxynaphthalene instead .1 of 4' buty1-1-hydroxynaphthe-lens.

Example 2 17.2 parts of 4-ethyl-l-hydroxynaphthalene and 200 parts of caustic soda solution of 30 per cent. strength are made into a paste while stirring and 25 parts of the diazo compound of 1- amino-2-hydroxynaphthalene 4 sulfonic acid are gradually added while stirring; the dark blue dyestuff paste is then allowed to stand over night, diluted with Water, salted out with sodium chloride and the dyestufi is then filtered off with suction. In the free state it corresponds to the formula OH OH GE -CH3 To be purified further, the dyestuff is again taken up in water, salted out with sodium chloride, filtered with suction and dried.

A dark powder is obtained which is soluble in water and dyes wool in the after-chroming process in reddish dark blue tints.

If 20 parts of 4-butyl-1-hydroxynaphthalene are used instead of 4-ethyl-l-hydroxynaphthalene, a similar dyestuff is obtained which dyes wool in the after-chroming process in dark blue tints of very good wet fastness properties and good fastness to light.

Example 3 100 parts of well wetted wool are introduced at a temperature of 60 C. into a dyebath containing, in 4000 parts of water, 1 part of the dyestufi obtained according to the first paragraph of Example 1, 2.5 parts of ammonium sulfate, 2.5 parts of sodium chromate and parts of Glauber salt. The temperature is raised to the boil Within 30 minutes and dyeing is carried out for 45 minutes at the boil. 0.5-1 per cent of acetic acid of 40 per cent. strength is then added and dyeing is continued for another hour, followed by rinsing and drying. The wool is dyed fast greenolive tints.

Example 4 100 parts of well wetted wool are introduced at 60 C. into a dyebath containing, in 4000 parts of water, 1 part of the dyestuff obtained according to the second paragraph of Example 1, 4 parts of acetic acid and 10 parts of Glauber salt. The temperature is raised to the boil within 30 minutes and dyeing is carried out for 45 minutes at the boil. 1 part of sulfuric acid of 66 B. is added and dyeing continues for another minutes at the boil, the dyebath is cooled down to about 70 C. 1 part of potassium bichromate is added, the temperature is raised to the boil and chroming is then carried out for about 40 minutes, followed by rinsing and drying. The wool is dyed fast blue-gray tints.

What we claim is:

1. An azo dyestuff which in its free state corresponds to the formula 10 on on s osn CHzCHaCHzCH! wherein it stands for a member selected from the group consisting of N02 and Cl. 0 2. The azo dyestuff of the formula on on scan I NO:

H2CH2CH2CH;

3. The azo dyestuff of the formula on OH soan so oHFom-oHr-om FRIEDRICH FELIX. ALPHONSE HECKENDORN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 303,335 Spiegel Aug. 12, 1884 1,314,921 Andrews Sept. 2, 1919 2,052,477 Krebser Aug. 25, 1936 r 2,090,938 Conrad Aug. 24, 1937 2,229,200 Wehrli Jan. 21, 1941 2,353,675 Kneoht et a1. July 18, 1944 2,405,816 Conzetti Aug. 13, 1946 FOREIGN PATENTS Number Country Date 771,420 France 

